KR20050071649A - Resin composition, transfer material and process for producing shaped item - Google Patents

Abstract

A thermosetting and actinic energy radiation hardenable resin composition, comprising a polymer of 100 to 300 g/eq (meth)acrylic equivalent, 50 to 550 mgKOH/g hydroxyl value, 7000 g/eq or more epoxy equivalent and 5000 to 100,000 weight average molecular weight and a heat hardening agent as active ingredients; a transfer material comprising a base sheet and, superimposed thereon, a protective layer constituted of a product of thermal crosslinking reaction of the resin composition; and a process for producing a shaped item, comprising first adhering this transfer material to a surface of shaped item or instead incorporating this transfer material in a metal mold and injecting a resin into the cavity of the mold so as to obtain a shaped item and simultaneously adhere the transfer material to a surface thereof, subsequently detaching the base sheet and thereafter exposing the shaped item surface to actinic energy radiation to thereby form a protective layer. Thus, there can be provided an actinic energy radiation hardenable resin composition which is obtained at low cost, excelling in wear and abrasion resistance and chemical resistance, and which is used in a protective layer of transfer material without cracking at curved portions of shaped item at the transfer, and further can be provided such a transfer material and a process for producing a shaped item.

Description

RESIN COMPOSITION, TRANSFER MATERIAL AND PROCESS FOR PRODUCING SHAPED ITEM}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a resin composition, a transfer material and a method for producing a molded article, and more particularly, a resin composition having a thermosetting property and an active energy ray curability having abrasion resistance, an aftercure transfer material using the same, and the The present invention relates to a method for producing a molded article excellent in wear resistance and chemical resistance using a transfer material.

Conventionally, as a method of forming a protective layer on the surface of a molded article, after a transfer material having a protective layer formed on a base sheet having a releasability is adhered to the surface of the molded article, and then peeling off the base sheet There is a law. In addition, the simultaneous transfer method of inserting the transfer material into a molding mold, injecting and filling a resin into a cavity, and cooling the resin to obtain a resin molded article, bonding the transfer material to the surface thereof, and then peeling off the gas sheet. There is this.

Generally as a protective layer of a transfer material, thermosetting resin, active energy ray hardening resin, etc. are used.

However, when a thermosetting resin is used as a protective layer and heated at the time of preparation of the transfer material to crosslink and cure the thermosetting resin, chemical resistance and abrasion resistance of the surface of the molded article after transferring to the molded article are generally inferior.

On the other hand, when the active energy ray curable resin is crosslinked and cured by irradiating the active energy ray during the preparation of the transfer material by using the active energy ray curable resin as the protective layer, the crosslinking density of the resin can be increased to improve wear resistance and chemical resistance. On the other hand, on the other hand, the protective layer is receded, so that a crack occurs in the protective layer disposed on the curved portion of the molded article at the time of transfer.

Thus, as another method of using an active energy ray-curable resin as a protective layer, the active energy ray is irradiated in a first step during the fabrication of the transfer material, and the active energy ray-curable resin is semi-hardened. By investigating this, the method of completely hardening the active energy ray curable resin used as a protective layer is examined.

However, since it is difficult to control the irradiation amount of the active energy ray and the control of the curing reaction, it is extremely difficult to obtain a suitable semi-cured state in the transfer material.

As a method of solving such a problem, an active energy ray-curable resin containing a specific polymer and polyfunctional isocyanate as an active ingredient has been proposed (for example, Japanese Patent Laid-Open No. 10-58895 and Japan). Japanese Patent Application Laid-Open No. 10-67047). In this resin type, an appropriate semi-cured state is achieved by addition reaction between hydroxyl groups in the polymer and polyfunctional isocyanates.

However, also in the above-mentioned active energy ray-curable resin, since the reaction between the hydroxyl group and polyfunctional isocyanate contained therein proceeds at room temperature, the useful time as the active energy ray-curable resin composition is short, and satisfactory resin compositions and transfer materials It is the present situation that is not realized.

The present invention has been made in view of the above problems, and it is possible to obtain a molded article excellent in wear resistance and chemical resistance at a low cost, and has a long usable period, and transfer which does not generate cracks (cracks) in the curved portion of the molded article at the time of transfer. An object of the present invention is to provide an active energy ray-curable resin composition which can be used as a protective layer of ash, a transfer material and a method for producing a molded article using the same.

According to the present invention, (meth) acrylic equivalent of 100 ~ 300g / eq, hydroxyl value (hydroxyl value) 50 ~ 550 mgKOH / g, epoxy equivalent of 7000g / eq or more, weight average molecular weight of 5000 ~ 100000 polymer and thermosetting agent This provides a resin composition having thermosetting and active energy ray-curing properties.

Moreover, according to this invention, the transfer material by which the protective layer is formed by the thermal crosslinking reaction product of the said resin composition on the gas sheet which has mold release property is provided.

Further, according to the present invention, after the transfer material is adhered to the surface of the molded article, or the transfer material is inserted into the molded article mold, resin is injected into the cavity to fill it to form a molded article, and the transfer material is adhered to the surface. After that, the substrate is peeled off, and the surface of the molded article is irradiated with an active energy ray to provide a method for producing a molded article that forms a protective layer on the surface of the molded article.

EXAMPLE

The resin composition of the present invention is a (meth) acrylic equivalent of 100 ~ 300 g / eq, hydroxyl value of 50 ~ 550 mgKOH / g, epoxy equivalent of 7000 g / eq or more, weight average molecular weight of 5000 ~ 100000 polymer and thermosetting agent as an active ingredient It is configured by. The said (meth) acryl means an acryl or methacryl. The (meth) acrylic equivalent is, for example, reacting a resin composition with a mixed solution of sodium bromide and potassium bromide, and titrating a mixture of potassium iodide solution with sodium thiosulfate solution using the starch solution as an indicator. Here's how. The hydroxyl value can be measured by, for example, reacting the resin composition with excess acetic anhydride in pyridine and titrating the desired acetic acid with potassium hydroxide. In addition, epoxy equivalent can be measured by the method of titrating the acetic acid solution of a polymer with the mixed solution of acetic acid and hydrogen bromide, for example. A weight average molecular weight can be calculated | required in polystyrene conversion by the gel permeation chromatography.

The polymer is in a specific formulation in consideration of the physical and chemical demand performance before and after active energy ray irradiation. That is, the (meth) acrylic equivalent is preferably about 100 to 300 g / eq from the viewpoints of curability at the time of active energy ray irradiation, abrasion resistance after active energy ray irradiation, and ease of actual synthesis, and about 150 to 300 g / eq. More preferred.

Moreover, the hydroxyl value of a polymer is suitably 50-550 mgKOH / g from a viewpoint of the reactivity with the thermosetting agent used together, the thermal crosslinking degree at the time of forming the protective layer of a transfer material, the ease of synthesis, etc., and 100-300 mgKOH. / g is more preferable. If the reaction with the thermosetting agent is insufficient or the thermal crosslinking degree is low, it is difficult to repeatedly print or roll up the transfer material due to the remaining adhesiveness or lack of solvent resistance in the manufacturing process of the transfer material. do.

The epoxy equivalent of the polymer is preferably 7000 g / eq or more from the viewpoints of the stability of the polymer, the suitability of coating, the curability upon irradiation with active energy rays, the wear resistance after irradiation with active energy rays, and the ease of synthesis in practice. Epoxy equivalent of 7000 g / eq or more means that an epoxy group exists in the molecule | numerator slightly, and is not contained to the extent which can substantially contribute to crosslinking of a polymer. When the epoxy equivalent is too small, it is easy to gelate during synthesis, and thus, the synthesis becomes difficult, and the curing resistance at the time of active energy ray irradiation and the wear resistance after active energy ray irradiation are reduced.

Moreover, in the manufacturing process of a transfer material, since adhesiveness remains or there is a lack of solvent resistance, it is not difficult to repeatedly print or wind up a transfer material, a clear patterned layer can be obtained, and the ink workability | operativity of a ink improves and it is suitable From a viewpoint of obtaining a viscosity, the weight average molecular weight of the polymer is preferably about 5000 to 100,000 in terms of polystyrene, and more preferably about 5000 to 50,000.

As the polymer as described above, for example, a reaction product in which monocarboxylic acid having an unsaturated double bond is added to a polymer having an epoxy group can be used. As a polymer which has an epoxy group, the homopolymer of glycidyl (meth) acrylate, the copolymer which consists of glycidyl (meth) acrylate, and the monomer which can superpose | polymerize with this is mentioned. As a monomer which can superpose | polymerize, (meth) acrylic acid ester, (meth) acrylamide, styrene, vinyl acetate, an acrylonitrile, etc. are mentioned, for example. As monocarboxylic acid which has an unsaturated double bond, (meth) acrylic acid, 2-methacryloxyethyl succinic acid, 2-methacryloxyethyl phthalic acid, 2-methacryloxyethyl hexahydro phthalic acid, etc. are mentioned, for example. Can be.

Moreover, as a polymer, (2) The reaction product which introduce | transduced the (meth) acryloyl group into a part of the side chain of the polymer containing a hydroxyl group, ③ The reaction product which condensed the polymerizable unsaturated monomer containing a hydroxyl group in the polymer containing a carboxyl group, (4) The reaction product etc. which added the polymerizable unsaturated monomer which has an epoxy group to the polymer containing a carboxyl group may be sufficient.

Here, as a polymer containing a hydroxyl group, hydroxyl-containing (meth) acrylate, specifically 2-hydroxyethyl (2-hydroxyethyl) (meth) acrylate, 2-hydroxypropyl (meth) acrylate, 4- Homopolymers or copolymers such as hydroxybutyl (meth) acrylate, and homopolymers or copolymers of ε-caprolactone adducts of hydroxyl group-containing (meth) acrylates.

As a polymer containing a carboxyl group, the homopolymer or copolymer of (meth) acrylic acid, the homopolymer or copolymer of 2-methacryloxyethyl succinic acid, such as the homopolymer or copolymer of 2-methacryloxyethyl phthalic acid, etc. The homopolymer or copolymer of methacryloxyethyl hexahydro phthalic acid, etc. are mentioned.

As a polymer unsaturated monomer which has a hydroxyl group, the hydroxyl-containing (meth) acrylate mentioned above, the (epsilon) -caprolactone adduct of these (meth) acrylates, etc. are mentioned.

As a polymerizable unsaturated monomer which has an epoxy group, glycidyl (meth) acrylate, 4-hydroxybutyl (meth) acrylate glycidyl ether, 3, 4- epoxycyclohexyl (meth) acrylate, etc. are mentioned. .

These polymers may be prepared according to a conventionally known method or in accordance with the method, so that the (meth) acrylic equivalent, hydroxyl value, epoxy equivalent, weight average molecular weight, etc. are within the above ranges, and the types of monomers and polymers used, these amounts of use, etc. It is necessary to select and adjust properly.

As a thermosetting agent, it is generally used as a crosslinking agent, and it is suitable that it is a thermosetting agent other than polyfunctional isocyanate. For example, one or more compounds selected from chelating compounds, metal alkoxides, silane coupling agents, partial hydrolyzates and acid anhydrides thereof, and the like can be mentioned. These types are not particularly limited and can be appropriately selected from known ones. Moreover, it is suitable that these compounds are not a compound containing 2 or more of isocyanate groups, More preferably, they are not a compound containing 1 or more. Moreover, as a thermosetting agent from another viewpoint, it is a compound which has a functional group or structure which can react with a hydroxyl group, and what has a functional group other than an isocyanate group is suitable. As such a functional group, an alkoxy group, an alkoxy silyl group, an acid anhydride group, etc. are mentioned, for example. Moreover, as a structure which can react with a hydroxyl group, (beta) -diketone and (beta) -ketoester coordinated with metal ion, these derivatives, etc. are mentioned.

Examples of the chelate compound include aluminum, titanium and zirconium, and as ligands, acetylacetone, ethyl acetoacetate, and mixtures thereof, which are β-diketones and β-ketoesters, are suitably used. Specifically, ethyl acetoacetate aluminum diisopropionate, aluminum tris (ethylacetoacetate), alkyl acetate acetate aluminum diisopropyrate, aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum tris (acetylacetonate), Diisopropoxybis (acetylacetonate) titanium, di-n-butoxybis (triethanol aluminate) titanium, and the like.

Examples of the metal alkoxide include metal alkoxides of aluminum, titanium, and zirconium. Specifically, aluminum methoxide, aluminum ethoxide, aluminum isopropoxide, aluminum sec-butoxide, titanium ethoxide, titanium Isopropoxide, titanium-n-butoxide, etc. are mentioned.

As a silane coupling agent, what has three or more alkoxy groups in 1 molecule is preferable, Specifically, tetraethoxysilane, tetraethoxysilane oligomer, tetramethoxy silane, tetramethoxysilane oligomer, methyltrimethoxysilane, ethyl Triethoxysilane, methyltriethoxysilane, phenyltriethoxysilane, vinyltrimethoxysilane, vinyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane , β- (3,4-epoxy cyclohexyl) ethyltrimethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-mercaptopropyltrimethoxysilane, tetraiso Propoxysilane, tetra-n-butoxysilane, tetraisopropoxysilane oligomer, tetra-n-butoxysilane oligomer, etc. are mentioned. Moreover, these silane coupling agents may be partially hydrolyzed. The method of hydrolysis can use a conventionally well-known method.

As an acid anhydride, what has two or more acid anhydride groups in 1 molecule is preferable, Specifically, a styrene maleic anhydride copolymer, (alpha)-olefin maleic anhydride copolymer, a pyromellitic dianhydride, benzophenone tetracarboxylic anhydride, methyl Cyclohexene tetracarboxylic anhydride etc. are mentioned.

Depending on the type of thermosetting agent, a catalyst may be used to promote the reaction. When the metal alkoxide or silane coupling agent is used as the thermosetting agent, the catalyst may be an alkali metal salt and an ammonium salt of carboxylic acid such as sodium acetate and ammonium acetate; chelate compounds of acetylacetone such as aluminum trisacetylacetonate and acetylacetone zirconium; Primary, secondary or tertiary amines such as butylamine, hydroxyethylamine, dimethylamine, diethylamine, trimethylamine, triethylamine, dimethylphenylamine, polyalkyleneamine; 2-methylimida; Imidazoles such as sol, 2,4-diethylimidazole, 2-phenylimidazole; metal salts and ammonium salts of perchloric acid such as magnesium perchlorate and ammonium perchlorate; metal salts of ethyl acetoacetate; acetylacetone and ethyl acetoacetate Metal salts; organometallic salts such as octylic acid tin; and the like. When an acid anhydride is used as a thermosetting agent, a catalyst is mentioned triphenylphosphine, tertiary amine, quaternary ammonium salt, an imidazole compound, etc.

It is suitable to mix | blend a polymer and a thermosetting agent in the ratio which becomes 1: 0.01-1: 0.8, Preferably it is 1: 0.05-1: 0.5 (weight ratio). Moreover, when using a catalyst, it is suitable to use a catalyst in the range of 0.1-20 weight% with respect to the weight of a polymer and a thermosetting agent.

Moreover, you may mix | blend a reactive monomer, a solvent, a coloring agent, etc. with the resin composition of this invention other than a polymer and a thermosetting agent as needed. In the case where the resin composition is cured by irradiating an electron beam during active energy ray irradiation, a sufficient effect can be obtained without using a photopolymerization initiator. However, when irradiating ultraviolet rays, a photopolymerization initiator and an accelerator as necessary. Preference is given to adding.

The reactive monomer is not particularly limited as long as it is capable of radical polymerization, but preferably has a functional group capable of radical polymerization of two or more in one molecule. As such a compound, neopentyl glycol di (meth) acrylate, 1, 6- hexanediol di (meth) acrylate, trimethylol propane tri (meth) acrylate, pentaerythritol tri (meth) acrylate, for example And (meth) acrylic acid esters such as pentaerythritol tetra (meth) acrylate and dipentaerythritol hexa (meth) acrylate.

Examples of the solvent include alcohols such as ethanol, isopropanol, butanol and benzyl alcohol; ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone; esters such as ethyl acetate, propyl acetate and butyl acetate; Aromatic hydrocarbons such as toluene and xylene; ethers such as diethyl ether, dioxane and tetrahydrofuran; ether alcohols such as ethoxyethanol, butoxyethanol and propylene glycol monomethyl ether.

A coloring agent is used in order to prevent a resin from becoming yellow at the time of active energy ray irradiation, etc. Generally, what is called a blueing agent can be used. For example, NICHILON BLUE GL, NICHILON BLUE 3GR (made by Nissei Kagaku) etc. are mentioned.

As a photoinitiator, it is 1-hydroxy cyclohexyl phenyl ketone, 2-hydroxy- 2-methyl- 1-phenylpropane- 1-one, 2-methyl- 1- [4- (methylthio) phenyl], for example. Acetophenone series initiators, such as -2-morpholino propane- 1-one and 1- [4- (2-hydroxyethoxy) phenyl] -2-hydroxy- 2-methyl- 1- propane- 1-one; Benzoin-type initiators, such as benzoin, 2, 2-dimethoxy- 1 and 2-diphenyl ethane- 1-one; benzophenone, [4- (methylphenylthio) phenyl] phenylmethanone, 4-hydroxybenzophenone Benzophenone initiators such as 4-phenylbenzophenone, 3, 3 ′, 4, 4′-tetra (t-butylperoxy carbonyl) benzophenone; 2-chloro thioxanthone, 2,4-diethyl tea Thioxanthone type initiators, such as oxanthone, etc. are mentioned.

As an accelerator, tertiary amines, such as p-dimethylamino benzoic acid ethyl ester and p-dimethylamino benzoic acid isoamyl ester, etc. are mentioned, for example.

Moreover, as mentioned later, when using a resin composition as a protective layer of a transfer material, it is preferable to contain a lubricant as needed. As a result, the surface of the protective layer is roughened to be easily rolled up as a sheet, blocking is less likely to occur, and resistance to friction and scratching can be increased.

Examples of the lubricant include waxes such as polyethylene wax, paraffin wax, synthetic wax, and montan wax; silicone resins such as polydimethylsiloxane and polyether-modified polydimethylsiloxane, and synthetic resins such as fluorine such as fluoroalkyl group-containing polymers. Can be mentioned. In the case of using a lubricant, in consideration of prevention of blocking, increase in resistance to frictional scratches, transparency of the resin composition itself, and the like, the amount of the resin composition is about 0.5 to 15% by weight, preferably 1 to 6% by weight. It is suitable to contain in the ratio of about%.

In order to impart functionality to the protective layer, a filler, an antistatic agent, a heat stabilizer, an optical stabilizer, an ultraviolet absorber, a near infrared ray blocker, or the like may be added to the resin composition. These substances may be used singly or in combination of two or more kinds depending on the function to be imparted.

As the filler, an inorganic substance and / or an organic substance can be used, and in particular, it is preferable to use an inorganic filler.

As said inorganic filler, silicon oxide, titanium oxide, zinc oxide, etc. are mentioned, for example. These may be in any form of fine particles, powder, slurry, or sol. By using a filler, blocking can be prevented and the hardness of a protective layer can be raised. In addition, the larger the particle diameter of the filler, the more effective the prevention of blocking, and the smaller the particle diameter, the more effective the hardness increase. Therefore, the particle diameter is suitably about several micrometers to several tens of micrometers when expecting a blocking prevention effect, and about several micrometers or less when expecting an increase of hardness.

As said antistatic agent, surfactant, a conductive filler, a conductive polymer, an ionic compound, etc. are mentioned.

As said surfactant, any of anionic, cationic, nonionic, and zwitterionic may be sufficient, and especially cationic surfactant is preferable.

Examples of the conductive filler include carbon black, antimony oxide, indium oxide, tin oxide, antimony dope tin oxide (ATO), indium dope tin oxide (ITO), and the like.

Examples of the conductive polymer include electron conduction types such as polypyrrole, polyanion, polyacetylene, and polythiophene, and ion conduction types such as anionic, cationic, and zwitterionic polymers. Nonionic polymers having a polyether skeleton can also be used as an antistatic agent.

As an ionic compound, a lithium ion salt is mentioned, for example. When using a lithium ion salt, it is preferable to use together the compound which has polyether skeletons, such as polyethyleneglycol.

Further, in order to have a sufficient antistatic effect, it is suitable that the surface resistance of the molded article 10 ⁶ ~ 10 ¹² Ω · cm, and preferably about adjustment about ^{10 7 ~ 10 11 Ω · cm} .

As a heat stabilizer, a hindered phenolic antioxidant, a phosphorus thermal stabilizer, a sulfur type thermal stabilizer, etc. are mentioned, for example.

As an optical stabilizer, a hindered amine light stabilizer etc. are mentioned, for example.

Examples of the ultraviolet absorber include benzotriazole-based, triazine-based, benzophenone-based and benzate-based ultraviolet absorbers.

As a near-infrared blocking agent, the organic pigment and dye excellent in shielding of near-infrared, or the pigment which absorbs near-infrared are mentioned, for example.

In the transfer material of the present invention, a protective layer is formed on a gas sheet having releasability by a thermal crosslinking reaction product of the resin composition.

Examples of the base sheet having a release property include resin sheets such as polypropylene resin, polyethylene resin, polyamide resin, polyester resin, polyacrylic resin, and polyvinyl chloride resin, aluminum foil, copper foil, and glassine. Usually used as a base sheet of a transfer material, such as a cellulose sheet, such as a paper, a coated paper, a cellophane, or a composite of each said sheet, can be used. Moreover, in order to improve the peelability of a base sheet, you may provide a release layer on the surface of a base sheet. The release layer is usually a layer which is peeled off together with the base sheet when the base sheet is peeled off after transfer or after simultaneous simultaneous transcription. For example, a melamine resin release agent, a silicone resin release agent, an acrylic resin release agent, a fluororesin release agent, and cellulose induction. It can be formed by a system release agent, a urea induction system release agent, a polyolefin resin-based release agent, a paraffin-based release agent and these complex release agents. The release layer can be formed by a coating method such as a gravure coating method, a roll coating method, a spray coating method, a lip coating method, a comma coating method, a gravure printing method or a screen printing method.

A protective layer can be formed by apply | coating the said resin composition on a base sheet by the above-mentioned coating method, printing method, etc., and hardening | curing. The film thickness of the protective layer is generally about 0.5 to 30 μm, preferably about 1 to 6 μm, in consideration of wear resistance, chemical resistance, cost of the protective layer forming material, sheet breakage of metal foil, and the like. It is suitable. It is preferable to perform hardening by heating a protective layer. As a result, the resin composition becomes a thermal crosslinking reaction product. The crosslinking reaction by heating is easier and advantageous than the crosslinking reaction by active energy ray irradiation. Therefore, the degree of thermal crosslinking can be suitably adjusted according to the kind of active energy ray-curable resin composition used, the thickness of a protective layer, the curvature of a molded article, etc. For example, it is suitable to perform about 10 to 120 second in the temperature range of about 100-200 degreeC. The resin composition of the present invention is not completely crosslinked and cured at the step of performing only thermal crosslinking. That is, it is semi-hardened and is tack-free. For this reason, the protective layer can be adapted to the curved surface of the molded article and has flexibility enough not to cause cracking, so that it is easy to print another layer on the protective layer or roll up the transfer material.

In addition, as described above, the protective layer may be provided with functionality, thereby reducing the number of layers to be processed, thereby improving product yield and reducing processing cost.

On the protective layer, at least one kind of various layers such as a functional layer to be transferred in a transfer material, for example, a pattern layer, an adhesive layer, an anchor layer, a low reflection layer, an antistatic layer, an ultraviolet absorbing layer, a near infrared shielding layer, and an electromagnetic wave absorbing layer. May be formed in any order. Especially, it is suitable to form an adhesive layer on the surface on the opposite side to a base sheet, and it is preferable to form a patterned layer and an adhesive layer in this order on a protective layer. Moreover, depending on the kind of functional layer, you may arrange | position a functional layer between a base sheet and a protective layer. These layers can be formed by a well-known material, a method, etc. For example, the functional layers and the formation method described in JP-A-10-58895, JP-A-11-123897, JP-A 2002-046207, WO01 / 92006, and the like can be used. .

Specifically, the patterned layer is usually formed as a printed layer on the protective layer. As the material of the printing layer, resins such as polyvinyl resin, polyamide resin, polyester resin, polyacrylic resin, polyurethane resin, polyvinyl acetal resin, polyester urethane resin, cellulose resin and alkyd resin As a binder, it is preferable to use the coloring ink which contains the pigment or dye of a suitable color as a coloring agent.

As a formation method of a pattern layer, normal printing methods, such as the offset printing method, the gravure printing method, the screen printing method, etc. can be used. In particular, an offset printing method or a gravure printing method is suitable for performing multicolor printing or gradation expression. In the case of a monochromatic color, you may use coating methods, such as the gravure coating method, the roll coating method, the comma coating method, and the lip coating method. The pattern layer can be formed entirely or partially depending on the pattern to be expressed. The pattern layer may be made of metal deposition or a combination of a printing layer and a metal deposition layer.

An adhesive layer adhere | attaches said each layer to the molded object surface. An adhesive layer is formed in the part to be bonded, such as on a protective layer or a pattern layer. That is, if the portion to be bonded is the entire surface, the adhesive layer may be formed on the entire surface, and if the portion to be bonded is partial, the adhesive layer may be partially formed.

As the adhesive layer, a thermosensitive or pressure-sensitive resin suitable for the raw material of the molded article can be used. For example, when the material of a molded article is polyacrylic-type resin, it is preferable to use polyacrylic-type resin. Moreover, in the case of the material of a molded article, polyphenylene oxide, polystyrene resin, polycarbonate resin, styrene copolymer resin, and polystyrene blend resin, polyacrylic resin, polystyrene resin, polyamide which are compatible with such resin It is good to use a system resin. Further, when the material of the molded article is polypropylene, chlorinated polyolefin resin, chlorinated ethylene-vinyl acetate copolymer resin, cyclized rubber, and coumarone-indene resin can be used.

As the method for forming the adhesive layer, the above-described coating method, printing method and the like can be used. In addition, when a protective layer or a patterned layer has sufficient adhesiveness with respect to a molded article, it is not necessary to form an adhesive layer.

The anchor layer is a resin layer for enhancing the adhesiveness between the transfer layers and protecting the molded article and the pattern layer from chemicals. For example, a two-component curable urethane resin, a thermosetting resin such as melamine or epoxy, and a vinyl chloride copolymer Thermoplastic resins, such as resin, can be used. The anchor layer can be formed using the above coating method, printing method, or the like.

In the method for producing a molded article of the present invention, first, the transfer material is adhered to the molded article surface, or the transfer material is inserted into a mold of the molded article, and resin is injected into the cavity to fill the molded article to form a molded article and at the same time. Bond the transfer material.

In the case of adhering the transfer material to the surface of the molded article, it is appropriate to superimpose the transfer material, preferably the adhesive layer side on the molded article, and apply pressure or heat pressure from the base sheet. The pressure or heat pressure from the base film can be performed using a heat-resistant rubber-like elastic body, for example, a transfer machine such as a roll transfer machine or an up-down transfer machine provided with a silicon rubber. In this case, the pressure is suitably about 5 to 200 kg / cm 2. In addition, it is preferable to heat the surface of the silicone rubber rubber to a temperature of about 80 to 250 ° C.

In addition, any injection molding mold can be used as long as it is normally used when manufacturing a resin molded article, and a pair of molding dies of a movable mold and a fixed mold can be mentioned, for example. Using such a molding die, the transfer material is placed inward, that is, the base sheet is placed in contact with the stationary mold. At this time, a single transfer material may be sent one by one, or the required portion of the long transfer material may be intermittently supplied. In the case of using a long elongated transfer material, it is preferable to use a transfer device having a positioning mechanism so that the scale of the transfer material, for example, the pattern layer and the molding die, is consistent. When the transfer material is intermittently sent, if the transfer material is fixed to the movable type and the fixed type after the position of the transfer material is detected by the sensor, the transfer material can always be fixed at the same position. This is advantageous because no position error occurs. After closing the molding die, the molten resin is injected into the mold from the gate provided in the movable mold to fill the mold, and at the same time, the transfer material is adhered to the surface thereof. After cooling the molded resin article, the molding die is opened to take out the molded resin article.

Thereafter, the base sheet is peeled off and the surface of the molded article is irradiated with an active energy ray. Thereby, the resin which comprises a protective layer crosslinks completely, and the protective layer which fully hardened on the surface of a molded article can be formed. In addition, after peeling a base sheet, you may irradiate an active energy ray, and after irradiating an active energy ray, you may peel a base sheet. When the base sheet is peeled off, peeling occurs at the interface between the base sheet and the protective layer. In the case where the release layer is formed on the base sheet, the base sheet is peeled off, and peeling occurs at the interface between the release layer and the protective layer.

As an active energy ray to irradiate, an electron beam, an ultraviolet-ray, etc. are mentioned, for example. The irradiation amount of an active energy ray can be suitably adjusted with the kind of resin composition used, the film thickness of a protective layer, etc., for example, about 50-1000mJ / cm <2> is mentioned. Thereby, a protective layer is arrange | positioned in the outermost layer of a molded article, and can protect functional layers, such as a molded article and a patterned layer, from chemicals and friction.

Here, the molded article is not particularly limited, but for example, a surface of a polarizing plate used for various displays such as word processors, computers, televisions, display panels, mobile phones, liquid crystal displays, and the like, and sunglass lenses made of transparent plastics And optical lenses such as eyeglass lenses with power, finder lenses of cameras, display sections of various instruments, and glass windows of automobiles and electric vehicles.

These molded articles include, in particular, resin molded articles, woodworking articles or these composite products. These may be either transparent, translucent, or opaque. Moreover, the molded article may be colored and does not need to be colored. The material is not particularly limited as long as it can form the surface of the polarizing plate, the optical lens, the display portion of various instruments, the glass window of the automobile, the electric vehicle, and the like, and for example, polystyrene resin, polyolefin resin, ABS resin, AS resin. And general purpose resins such as AN resin. Moreover, polyphenylene oxide polystyrene resin, polycarbonate resin, polyacetal resin, acrylic resin, polycarbonate modified polyphenylene ether resin, polyethylene terephthalate resin, polybutylene terephthalate resin, ultra high molecular polyethylene resin, etc. Super engineering plastics such as general-purpose engineering plastics, polysulfone resins, polyphenylene sulfide resins, polyacrylate resins, polyetherimide resins, polyimide resins, liquid crystal polyester resins, polyallyl heat-resistant resins and cycloolefin resins Can be used. Moreover, the composite water which added reinforcing agents, such as glass fiber and an inorganic filler, may be sufficient. These materials may be used independently and may be used in combination of 2 or more.

EMBODIMENT OF THE INVENTION Below, the manufacturing method of the resin composition, the transfer material, and the molded article of this invention is demonstrated in detail based on an Example. In addition, "part" and "%" shown below are a basis of weight. The (meth) acrylic equivalent was measured by reacting the polymer with a mixed solution of sodium bromide and potassium bromide, followed by titration with a sodium thiosulfate solution using a starch solution as an indicator. The hydroxyl value was measured by the method of reacting a polymer with excess acetic anhydride in pyridine and titrating advantageous acetic acid with potassium hydroxide. The epoxy equivalent was measured by titrating the acetic acid solution of the polymer with a mixed solution of acetic acid and hydrogen bromide. The weight average molecular weight of the polymer was calculated in terms of polystyrene by gel permeation chromatography.

Example 1 Synthesis of Thermosetting and Active Energy Line Curable Polymer Solution A

In a reactor equipped with a stirring device, a cooling pipe, and a nitrogen introduction pipe,

Glycidyl methacrylate (hereinafter abbreviated as GMA) 35 parts

15 parts of methyl methacrylate (hereinafter abbreviated as MMA)

Dodecyl mercaptan 0.3 part

1.5 parts of 2,2'- azoisobutyronitrile (it abbreviates as AIBN hereafter)

Butyl acetate 200 parts

After the addition, the mixture was heated up to 90 ° C. over about 1 hour under a nitrogen stream and kept warm for 1 hour. Then, in advance,

GMA 105

MMA Part 45

Dodecyl Mercaptan 0.7

AIBN Part 2

The mixed liquid which consisted of the mixed liquid which consisted of this was dripped over about 2 hours under nitrogen stream, it hold | maintained at 90 degreeC for 3 hours, and then, 2 parts of AIBNs were added, and it heated for 1 hour. Then, it heated up at 120 degreeC and kept warm for 2 hours.

After cooling to 60 ° C, replace the nitrogen inlet tube with the air inlet tube,

Acrylic acid (hereinafter abbreviated as AA) 71 parts

Metoquinone 0.4

Triphenyl phosphine part 1

Was added and mixed, and the temperature was raised to 110 ° C. under air bubbling, and the temperature was kept for 8 hours. Thereafter, 0.3 part of metoquinone was added and cooled, ethyl acetate was added so as to have a nonvolatile content of 50% to obtain a polymer solution A.

The polymer contained in the said polymer solution was acrylic equivalent 270g / eq, hydroxyl value 207mgKOH / g, epoxy equivalent 8000g / eq, and weight average molecular weight 20000.

Example 2 Synthesis of Thermosetting and Active Energy Line Curable Polymer Solution B

The amount of monomer used in the initial feeding in Example 1 was 45 parts of GMA and 5 parts of MMA, and the amount of monomer used in the subsequent feeding was replaced with 135 parts of GMA and 15 parts of MMA, and 92 parts of AA were used. In the same manner as in Example 1, polymer solution B was obtained.

The polymer contained in the polymer solution obtained above was acryl equivalent 230g / eq, hydroxyl value 240mgKOH / g, epoxy equivalent 10000g / eq, and weight average molecular weight 17000.

Example 3 Preparation of Thermosetting and Active Energy Line Curable Resin Composition C

Polymer solution A '200 parts (100 parts as a solid)

Aluminum trisacetylacetone 10 parts

Photopolymerization initiator (IRGACURE 184, manufactured by Ciba Specialty Chemicals, hereinafter

Equal) 5 copies

The resin composition C was obtained by mixing.

Example 4 Preparation of Thermosetting and Active Energy Line Curable Resin Composition D

Polymer solution B 200 parts (100 parts as solid content)

Tetraethoxysilane 10 parts

Aluminum trisacetylacetonate 5 parts

Photopolymerization initiator (IRGACURE 184) 7

The resin composition D was obtained by mixing.

Example 5 Manufacture of Transfer Material 1

Using a 38-micrometer-thick polyester film as a base sheet, the melamine resin type mold release agent was apply | coated to the thickness of 1 micrometer by the gravure printing method, and the release layer was formed on the base sheet.

On it, the protective layer which consists of resin composition C was formed by the gravure printing method. The film thickness of a protective layer was 5 micrometers. By heating at 150 degreeC for 30 second, the protective layer was semi-hardened, acrylic ink as a pattern layer, and acrylic resin as a contact bonding layer were formed sequentially by the gravure printing method, and the transfer material 1 was obtained.

Example 6 Manufacture of Transfer Material 2

Transfer material 2 was obtained in the same manner as in Example 5 except that resin composition D was used as the resin composition, and an anchor layer was formed to form a urethane ink.

Example 7: Preparation of Molded Article 1

Using the transfer material 1 of Example 6, and transferring to the surface of a molded article using the molding simultaneous transfer method, the base sheet was peeled off and irradiated with ultraviolet rays to completely crosslink and cure the protective layer. In addition, molding conditions were made into the resin temperature of 240 degreeC, the mold temperature of 55 degreeC, and the resin pressure of about 300 kg / cm <2>. The molded article was made of acrylic resin and molded into a tray shape having a length of 95 mm, a width of 65 mm, a height of 4.5 mm, and a corner portion of R2.5 mm. Ultraviolet irradiation conditions were 120 W / cm, 6 lamps, 10 cm in height of the lamp, and a belt speed of 15 m / min.

Example 8 Manufacture of Molded Article 2

It carried out similarly to Example 7 except having used the transfer material 2 of Example 6, the ultraviolet irradiation conditions being 120W / cm, 2 lamps, the height of a lamp 10cm, and belt speed 2.5m / min.

Comparative Example 1

The protective layer containing the silicone resin was formed by the gravure printing method, and then the protective layer was completely crosslinked and cured by heating at the time of preparation of the transfer material, and the same as in Examples 5 and 7, except that no ultraviolet rays were irradiated after the transfer. The molded article was formed.

Comparative Example 2

70 parts of urethane acrylate (UA-306H, manufactured by Kyoeisha Chemical Co., Ltd.)

30 parts of reactive monomer (light acrylate TMP-A, manufactured by Kyoeisha Chemical Co., Ltd.)

Photopolymerization initiator (IRGACURE 184) part 5

Example 5 and 7 except that the composition consisting of a protective layer and formed by the gravure printing method, completely cured the protective layer by ultraviolet irradiation at the time of manufacturing the transfer foil, and not irradiated with ultraviolet rays after the transfer In the same manner as the molded article was formed.

Ultraviolet irradiation conditions at the time of preparation of the transfer material were 120 W / cm, 2 lamps, lamp height 10 cm, and belt speed 20 m / min.

Comparative Example 3

The amount of the monomer used during the initial feeding in Example 1 was changed to 25 parts of GMA and 25 parts of MMA, and that the amount of used monomer was changed to 75 parts of GMA and 75 parts of MMA instead of 75 parts of GMA and 75 parts of MMA. A thermosetting and active energy ray-curable polymer solution E was obtained in the same manner as in Example 1, and a thermosetting and active energy ray-curable resin composition F was obtained in the same manner as in Example 3 except that this polymer solution E was used.

Except having used the composition which consists of said resin composition F as a protective layer, it carried out similarly to Example 5 and 7, and formed the molded article.

The polymer had an acrylic equivalent weight of 350 g / eq, a hydroxyl value of 155 mgKOH / g, an epoxy equivalent weight of 10000 g / eq, and a weight average molecular weight of 19000.

Comparative Example 4

A thermosetting and active energy ray-curable polymer solution G was obtained in the same manner as in Example 1 except that the amount of AA in Example 1 was set to 67 parts, and the same procedure as in Example 3 except that the polymer solution G was used. To obtain the resin composition H.

Except having used the composition which consists of said resin composition H as a protective layer, it carried out similarly to Example 5 and 7, and formed the molded article.

The polymer was an acrylic equivalent of 280 g / eq, a hydroxyl value of 190 mg KOH / g, an epoxy equivalent of 6000 g / eq, and a weight average molecular weight of 50000. Moreover, this polymer had a viscous stain.

Comparative Example 5

Active energy ray curable polymer solution A 200 parts

                                (100 parts as solid)

Polyfunctional isocyanate (Colonate HX, Japan Polyurethane Industry Co., Ltd.) 10 parts

Photopolymerization initiator (IRGACURE 184) 184 Part 5

By mixing, thermosetting and active energy ray curable resin composition I was obtained.

Except having used the composition which consists of said resin composition I as a protective layer, the molded article was created like Example 5 and 7.

Test Example

About Example 7, 8 and Comparative Examples 1-5, the film characteristics, the presence or absence of a crack, chemical resistance, abrasion resistance, and usable time were evaluated, respectively.

① Coating characteristics: The coating characteristics of the resin composition at the time of preparation of the transfer material are judged by visual inspection to indicate that the coating film is smooth, ○, that a little streaks occur, △, and that streaks occur throughout the entire surface, indicated by ×. It was.

(2) The presence or absence of a crack: The curved state of the molded product was observed, and judged by visual inspection, (circle) and the occurrence of a crack were marked as (circle), a little (triangle | delta), and generation | occurence | production significantly was represented by x.

(3) Chemical resistance: The surface state after impregnating methanol with gauze and rubbing 50 times round and round was judged by visual inspection, and it showed that there was no change, (circle white) was (triangle | delta), and the whole white was represented by x.

④ Abrasion resistance: Using steel wool of # 0000, apply loads of 100g / cm2 and 300g / cm2 and visualize the degree of scratch on the surface after 10 round trips with 2cm travel and 2 round trips / second. Judging by the inspection, (circle) that there were only a few wounds, (circle) that several dozen wounds were made, (triangle | delta) and the thing with the wound which appeared in the whole surface were marked with x.

⑤ Usable time: The resin composition was placed in a constant temperature bath at 40 ° C. and the temporary service time was measured. Temporary use time was made into the time when the viscosity of liquid multiplied initially. The obtained results are shown in Table 1.

TABLE 1

Film characteristics crack Chemical resistance Wear resistance Available time 100g / ㎠ 300g / ㎠ Example 7 ○ ○ ○ ○ ○ More than 24 hours Example 8 ○ ○ ○ ○ △ More than 24 hours Comparative Example 1 ○ △ △ △ △ - Comparative Example 2 ○ × ○ ○ ○ - Comparative Example 3 ○ ○ ○ × × - Comparative Example 4 × ○ ○ ○ △ 12 hours or less Comparative Example 5 ○ ○ ○ ○ ○ 8 hours or less

According to the said Table 1, Example 7 and 8 are excellent in abrasion resistance and chemical-resistance, and the crack did not generate | occur | produce about the curved part of a molded article. In contrast, in Comparative Example 1, cracks, abrasion resistance, and chemical resistance were not all satisfactory. Although Comparative Example 2 was excellent in terms of wear resistance and chemical resistance, many cracks were generated. In Comparative Example 3, no crack was generated, but the abrasion resistance was not satisfactory. In Comparative Example 3, since the acrylic equivalent of the polymer contained in the active energy ray-curable resin composition exceeds a specific range, wear resistance is inferior. In the comparative example 4, since the epoxy equivalent was out of the specific range, the film characteristic was bad and the stability of the composition was bad. In Comparative Example 5, the stability of the resin composition was poor, and the temporary service time was short.

On the other hand, the transfer material used in Examples 7 and 8 had a temporary use time such that the resin composition constituting the protective layer could withstand practical use.

According to the present invention, by blending a specific resin composition, it is possible to provide a resin composition having better wear resistance, chemical resistance, temporary service life, and the like by curing in two stages.

Therefore, when using such a resin composition for the protective layer of a transfer material, the protective layer is semi-hardened by primary hardening, realizing the distribution as a transfer material, without degrading the quality, and the transfer. After the ash is used in the manufacture of the molded article and adhered to the surface of the molded article, the molded article excellent in low cost, wear resistance, chemical resistance and the like can be produced by completely curing the resin by secondary curing. In particular, even when there is a complicated curved surface on the surface of the molded article, generation of cracks in the curved portion can be prevented.

Claims (9)

(Meth) acrylic equivalent 100-300g / eq, hydroxyl value 50-550mgKOH / g, epoxy equivalent 7000g / eq or more, the weight average molecular weight 5000-100000 polymer, and a thermosetting agent characterized by containing a thermosetting agent as an active ingredient, and A resin composition having active energy ray curability. The method of claim 1, A resin composition wherein the polymer is a reaction product obtained by adding a monocarboxylic acid having an unsaturated double bond to a polymer having an epoxy group. The method of claim 2, The resin composition whose polymer which has an epoxy group is a homopolymer of glycidyl (meth) acrylate or a copolymer of glycidyl (meth) acrylate. The method according to any one of claims 1 to 3, A resin composition wherein the thermosetting agent is at least one compound selected from the group consisting of chelating compounds, metal alkoxides, silane coupling agents, partial hydrolyzates and acid anhydrides thereof. The method according to any one of claims 1 to 4, Resin composition containing a photoinitiator. A protective material is formed on a gas sheet having a release property by a thermal crosslinking reaction product of the resin composition according to any one of claims 1 to 5. The method of claim 6, A transfer material in which a pattern layer and an adhesive layer are formed in this order on a protective layer. A protective layer is formed on the surface of the molded article by adhering the transfer material according to claim 6 or 7 to the surface of the molded article, and then peeling off the gas sheet and irradiating active energy rays to the surface of the molded article. The manufacturing method of the molded article made into. The transfer material according to claim 6 or 7 is inserted into a molded product mold, the resin is injected into the cavity to be filled to form a molded product, the transfer material is adhered to the surface thereof, and then the gas sheet is peeled off. A protective layer is formed on the surface of the molded article by irradiating an active energy ray on the surface of the molded article.